CN102791759B - Polyurethane resin - Google Patents
Polyurethane resin Download PDFInfo
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- CN102791759B CN102791759B CN201180014077.9A CN201180014077A CN102791759B CN 102791759 B CN102791759 B CN 102791759B CN 201180014077 A CN201180014077 A CN 201180014077A CN 102791759 B CN102791759 B CN 102791759B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Disclosed is a solvent-free polyurethane resin that has superior adhesive properties, physical properties, handling properties and storage stability properties and can be used suitably in curable compositions having the physical properties of a low modulus and high elongation after curing. Also disclosed is a method for producing this polyurethane resin easily and inexpensively. The average number of terminal hydroxyl groups in this polyurethane resin is 1.3 - 2.1, and the polyurethane resin is obtained by reacting a urethane prepolymer, which is obtained by reacting a mixture of a mono-ol and polyol with a polyisocyanate, and a compound having cross-linked silyl groups as well as imino groups and amino groups.
Description
Technical field
Present patent application is advocated right of priority to Japanese patent application No. 2010-60779 (March 17 2010 applying date), at this, by reference, the whole of them is brought in this specification sheets.
The present invention relates to a kind of urethane resin, specifically, relate to no-solvent type urethane resin and manufacture method thereof, described no-solvent type urethane resin can perform well in the solidification compound of the physical property with low modulus, high elongation rate, and has excellent tackiness, physical property, disposal and package stability.
Background technology
In the past, known by addition endways in molecule, have amino silane compound carbamate prepolymer manufacture and urethane resin owing to thering is amino-formate bond and urea bond in molecular chain, therefore there is excellent physical property, for example, there is excellent ductility and obdurability (patent documentation 1 and 2).But, for above-mentioned urethane resin, because the secondary amino group remaining in prepolymer makes prepolymer present alkalescence, therefore can advance the hydrolysis of alkoxysilyl, produce thus gelation or tackify, thereby have the problem that lacks package stability.
Therefore, present alkaline amino method as elimination, following method was proposed,, to alpha-beta-beta-unsaturated carbonyl compounds, addition has amino silane compound and forms after alkoxysilane compound containing trialkylsilyl group in molecular structure, added to by (patent documentation 3) on carbamate prepolymer.But, in the case of utilizing above-mentioned method to produce the urethane resin of low modulus and high elongation rate, can cause the deterioration of high viscosity and the property disposed of this urethane resin, and its manufacturing process's complexity and cost high.
Patent documentation
Patent documentation 1: Japanese kokai publication hei 03-047825 communique
Patent documentation 2: Japanese kokai publication hei 03-157424 communique
Patent documentation 3: Japanese kokai publication hei 2000-169544 communique
Summary of the invention
Invent technical problem to be solved
The object of the invention is to, a kind of no-solvent type urethane resin is provided and easily and at an easy rate manufactures the method for this urethane resin, physical property after described no-solvent type urethane resin can perform well in solidifying is the solidification compound of low modulus, high elongation rate, and has good tackiness, physical property, disposal and package stability.
The means of dealing with problems
The discoveries such as the inventor, mixture that to make average terminal hydroxyl number be 1.3～2.1, single methanol and polyvalent alcohol reacts with polymeric polyisocyanate, thereby obtain carbamate prepolymer, by making this carbamate prepolymer, reacting and obtain urethane resin with the compound in molecule with bridging property silyl and imino-and amino, utilize this urethane resin to address the above problem, thereby completed the present invention.
,, in the present invention, comprise preferred embodiment following.
[1] urethane resin, it is to obtain by making to have bridging property silyl, imino-and amino compound reaction in (1) carbamate prepolymer and (2) molecule,
By making, (a) average terminal hydroxyl number is 1.3～2.1 to described (1) carbamate prepolymer, the mixture of single methanol and polyvalent alcohol, and (b) polymeric polyisocyanate reaction obtains,
In described (2) molecule, there is bridging property silyl, imino-and amino compound and represented by following (formula 1),
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, R
1represent methyl or ethyl, R
2represent the alkyl of carbon number 2～10, R
3represent the alkyl of carbon number 2～10.
[2] according to the urethane resin [1] described, wherein, the number-average molecular weight of polyvalent alcohol (Mn) is 500～30000.
[3] according to the urethane resin [1] or [2] described, wherein, polyvalent alcohol is polyoxypropyleneglycol.
[4] according to the urethane resin described in any one in [1]～[3], wherein, in the scope that is 1.6～2.5 in the equivalence ratio of NCO/OH, carry out the mixture (a) of single methanol and polyvalent alcohol and reacting of polymeric polyisocyanate (b).
[5] according to the urethane resin described in any one in [1]～[4], wherein, at NCO/NH
2the equivalence ratio scope that is 0.6～1.2 in, carry out reacting of compound that described prepolymer represents with (formula 1).
[6] manufacture method for urethane resin, is characterized in that,
Make to there is bridging property silyl, imino-and amino compound reaction in (1) carbamate prepolymer and (2) molecule, wherein,
By making, (a) average terminal hydroxyl number is 1.3～2.1 to described (1) carbamate prepolymer, the mixture of single methanol and polyvalent alcohol, and (b) polymeric polyisocyanate reaction obtains,
In described (2) molecule, there is bridging property silyl, imino-and amino compound and represented by following (formula 1),
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, R
1represent methyl or ethyl, R
2represent the alkyl of carbon number 2～10, R
3represent the alkyl of carbon number 2～10.
Invention effect
Urethane resin of the present invention, owing to having excellent tackiness, physical property, disposal and package stability, therefore can be used as well tackiness agent and use.In addition, this urethane resin is owing to having low viscosity, therefore can not use solvent and well as tackiness agent.In addition, manufacturing method according to the invention, owing to not needing to make the operation of amino inerting, therefore can be cheap and manufacture simply above-mentioned urethane resin.
Embodiment
Below, embodiments of the present invention are described.
The present invention be make in (1) carbamate prepolymer and (2) molecule, to there is bridging property silyl, imino-and amino compound reaction and the urethane resin that makes, by making, (a) average terminal hydroxyl number is 1.3～2.1 to described (1) carbamate prepolymer, the mixture of single methanol and polyvalent alcohol, and (b) polymeric polyisocyanate reaction obtains, in described (2) molecule, having bridging property silyl, imino-and amino compound is represented by following (formula 1)
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, R
1represent methyl or ethyl, R
2represent the alkyl of carbon number 2～10, R
3represent the alkyl of carbon number 2～10.
Urethane resin of the present invention, because the average terminal hydroxyl number of the mixture (a) of single methanol and polyvalent alcohol is 1.3～2.1, and presents excellent physical property and stability.
In the present invention, average terminal hydroxyl is measured according to JIS K 1557-1:2007.
In the present invention, for the mixture (a) of above-mentioned single methanol and polyvalent alcohol, from the viewpoint of physical property and stability, using this mixture (a) total amount as benchmark, can be by making to be preferably 20 % by weight～80 % by weight, the single methanol of 35 % by weight～65 % by weight more preferably, be preferably 20 % by weight～80 % by weight, more preferably the polyvalent alcohol of 35 % by weight～65 % by weight is obtained by mixing.
As above-mentioned single methanol, for example can enumerate polyoxyalkylene single methanol, polyester single methanol, polyether ester single methanol, senior saturated single methanol, there is single methanol of alkene unsaturated double-bond etc., can use the one kind or two or more mixture in them.
As above-mentioned polyoxyalkylene single methanol, for example can enumerate the polyoxyalkylene that contains the high molecular of 1 hydroxyl at molecule obtaining as described below is single methanol,, the described polyoxyalkylene that contains the high molecular of 1 hydroxyl at molecule is that single methanol is using alkylate that contains 1 active hydrogen etc. as initiator, makes the epoxy alkane such as oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) carry out ring opening polyaddition and obtains.
As above-mentioned polyester single methanol, can enumerate: the alkylation modification thing of the terminal hydroxyl of known polyester polyol; Using monohydroxy compound as initiator, make annular lactone compound carry out the reaction of open loop addition copolymerization or esterification and lactone be polyester single methanol; Utilize polyvalent alcohol and saturated fatty acid or there is the carboxylic acid of alkene unsaturated double-bond and ester single methanol of obtaining etc.; Wherein, described in there is alkene unsaturated double-bond carboxylic acid be (methyl) vinylformic acid, styracin, or more than 10 higher unsaturated fatty acid of carbon number, that is, oleic acid, linolic acid, linolenic acid etc.
As above-mentioned polyether ester single methanol, can enumerate make fatty acid ester single methanol and aforementioned (list) epoxy alkane carry out addition polymerization and polyoxyalkylene fatty acid ester single methanol etc.
Wherein, from the viewpoint of versatility and security, be preferably polyoxyalkylene single methanol, be particularly preferably polyoxytrimethylene single methanol.
As the example of the commercially available product of above-mentioned single methanol, for example, can enumerate the PML-S1006 processed of Asahi Glass Co., Ltd etc.
As above-mentioned polyvalent alcohol, for example can enumerate polyvalent alcohols such as making ethylene glycol, propylene glycol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, sucrose, carry out addition polymerization with the epoxy alkane such as propylene oxide or propylene oxide and oxyethane and polyether glycol class; Ethylene glycol, propylene glycol and their oligomeric diol class; Butyleneglycol, hexylene glycol, polytetramethylene ether glycol class; Polycaprolactone polyol class; The polyester polyols alcohols of polyethylene adipate and so on; Polybutadiene polyol class; The high-grade aliphatic ester class with hydroxyl of Viscotrol C and so on; By vinyl monomer-grafted in polyether glycol class or polyester polyols alcohols and polymer polyatomic alcohol class etc.; Can use their one kind or two or more mixture.
Consider from the viewpoint of operability, solidified nature transitivity, above-mentioned polyvalent alcohol is preferably the polyoxyalkylene polyol as the affixture of propylene oxide or propylene oxide and oxyethane.Especially be used as the polyoxyalkylene polyol of the affixture of propylene oxide to be used as above-mentioned polyvalent alcohol, that is, polyoxypropylene polyol, especially polyoxypropyleneglycol are preferred in practical.
These polyvalent alcohols can utilize in the past known method manufacture, specifically, can exemplify the method for recording in No. 3076032 communique of Japanese Patent.
As the example of the commercially available product of above-mentioned polyoxyalkylene polyol, for example, can enumerate the PML-4011F processed of Asahi Glass Co., Ltd, PML-4013F etc.
In the present invention, for the number-average molecular weight (Mn) of above-mentioned single methanol, from the viewpoint of its cost or viscosity, be preferably more than 500, more preferably more than 1000.In addition, for the number-average molecular weight (Mn) of above-mentioned single methanol, from the viewpoint of the viscosity of the urethane resin of gained, be preferably below 25000, more preferably below 10000.
For the number-average molecular weight (Mn) of above-mentioned polyvalent alcohol, from the viewpoint of the physical property of the urethane resin of gained, be preferably more than 500, more preferably more than 1000.In addition, for the number-average molecular weight (Mn) of above-mentioned polyvalent alcohol, consider from the viewpoint of the viscosity of the urethane resin of gained, be preferably below 30000, more preferably below 20000.
At this, the number-average molecular weight (Mn) in the present invention and weight-average molecular weight (Mw) are the polystyrene conversion values of utilizing gel permeation chromatography (GPC) to record.
In addition, in the present invention, polymeric polyisocyanate (b) is reacted with the mixture (a) of above-mentioned single methanol and polyvalent alcohol.
As above-mentioned polymeric polyisocyanate, can enumerate aromatic poly-isocyanate (tolylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, Xylene Diisocyanate, tolidine vulcabond etc.), alicyclic polymeric isocyanate (dicyclohexyl methane diisocyanate, isophorone diisocyanate, isopropylidene two (4-cyclohexyl isocyanate), hydrogenated xylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate etc.), aliphatic polymeric isocyanate (hexamethylene diisocyanate, lysinediisocyanate, 2, 2, 4-trimethyl hexamethylene diisocyanate and 2, 4, 4-trimethyl hexamethylene diisocyanate etc.) etc., wherein, from the viewpoint of the xanthochromia of the urethane resin of gained, preferred aliphat and alicyclic polymeric isocyanate.
As the example of the commercially available product of above-mentioned polymeric polyisocyanate, for example, can enumerate the Desmodur I processed of Bayer company (IPDI), Desmodur H (HDI) etc.
In the present invention, so that the equivalence ratio of NCO/OH is preferably 1.6～2.5, more preferably 1.8～2.2 mode, the mixture (a) of single methanol and polyvalent alcohol is reacted with polymeric polyisocyanate (b).Said mixture (a) is reacted in above-mentioned scope with polymeric polyisocyanate (b), is being very favourable aspect the physical property of urethane resin and stability.
This reaction as required can such as, at suitable catalysts (the bismuth series catalysts, 1 such as organotin series catalysts, Bismuth Octoate such as dibutyl tin laurate, the tertiary amine series catalysts such as 4-diaza [2.2.2] double-octane) existence under, conventionally for example, under normal temperature～90 DEG C (60～90 DEG C), carry out with the condition of 1～48 hour.
Above-mentioned carbamate prepolymer (1) is the prepolymer (hereinafter referred to as end NCO prepolymer) that contains endways isocyanate group, for this end NCO content, from the viewpoint of the flexibility of the package stability of prepolymer, cured article, be preferably 0.2～6.0 % by weight, more preferably 0.4～4.5 % by weight.
In addition, the number-average molecular weight of above-mentioned end NCO prepolymer is generally 500～30000, from the viewpoint of the disposal of urethane resin, be preferably 1000～20000.
Urethane resin of the present invention can be by making above-mentioned carbamate prepolymer (1) react to manufacture with the compound (2) that (formula 1) by following represents,
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, preferably represents methyl, R
1represent methyl or ethyl, preferably represent methyl, R
2represent the alkyl of carbon number 2～10, preferably represent alkylidene group, R
3represent the alkyl of carbon number 2～10, preferably represent alkylidene group.
As the compound being represented by above-mentioned (formula 1), can enumerate aminoethylamino propyl group methyl dimethoxysilane, aminoethylamino propyl group methyltrimethoxy silane, aminoethylamino propyl group methyldiethoxysilane, aminoethylamino propyl group Union carbide A-162 etc., wherein, from the viewpoint of physical property, preferably aminoethylamino propyl group methyl dimethoxysilane, aminoethylamino propyl group methyltrimethoxy silane.
As the example of commercially available product of the compound being represented by above-mentioned (formula 1), for example, can enumerate the KBM-602 processed of KCC of SHIN-ETSU HANTOTAI, KBM-603 etc.
Urethane resin of the present invention can pass through so that NCO/NH
2equivalence ratio preferably become 0.6～1.2, more preferably become 1.0～1.2 mode, make above-mentioned carbamate prepolymer (1) and the compound (2) that represented by above-mentioned (formula 1) reacts and makes.Above-mentioned carbamate prepolymer (1) is reacted in above-mentioned scope with the compound being represented by above-mentioned (formula 1), very favourable aspect stability.
Urethane resin of the present invention as required can with common added ingredients, for example weighting agent, softening agent, tackifier, thixotropic agent, protective agent, water-retaining agent, prevent dropping down agent, leveling agent, UV light absorber, antioxidant, the mixing such as tackifier and curing catalysts, making can be at tackiness agent, sealing material, (carbamate is coating film waterproof material to elastomer material, carbamate is outer wall coating material, carbamate is coated floor material, carbamate is electric wire coating material, carbamate based elastomers formed material) etc. in use solidification compound.
As above-mentioned weighting agent, water-ground limestone, fatty acid treatment calcium carbonate, magnesiumcarbonate, diatomite be can enumerate, clay, clay burnt till, or granulated glass sphere, volcanic ash micropartical, glass sphere, silica spheres, baton round, powder coating baton round etc. are ball, talcum, titanium oxide, wilkinite, organobentonite, ferric oxide, zinc oxide, hydrogenated castor oil, asbestos, glass fibre etc., wherein, be preferably water-ground limestone.Using urethane resin of the present invention as solidification compound in the situation that, taking this solidification compound total amount as benchmark, the weighting agent that contains 0～70 % by weight.
As above-mentioned softening agent, can enumerate the phthalic esters such as dioctyl phthalate (DOP), dibutyl phthalate, butyl benzyl phthalate; The aliphatic carboxylic acid esters,s such as Octyl adipate, succsinic acid isodecyl ester, Uniflex DBS, butyl oleate; The diol-lipids such as pentaerythritol ester; The phosphoric acid ester such as dioctylphosphoric acid ester, trioctyl phosphate, Tritolyl Phosphate; The epoxy plasticizer such as epoxidised soybean oil, epoxystearic acid benzyl ester; Clorafin etc.; Wherein, preferred phthalic acid diisononyl esters.Using urethane resin of the present invention as solidification compound in the situation that, taking this solidification compound total amount as benchmark, the softening agent that contains 0～70 % by weight.
As above-mentioned tackifier, can enumerate N-(beta-aminoethyl)-N '-(γ-trimethoxy-silylpropyl)-quadrol, N-(beta-aminoethyl)-aminoalkoxy silane such as gamma-amino propyl trimethoxy silicane; Vinyltriethoxysilane, vinyltrimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) the oxirane TMOS such as ethyl trimethoxy silane etc., be wherein preferably amino silane compounds.Using urethane resin of the present invention as solidification compound in the situation that, taking this solidification compound total amount as benchmark, the tackifier that contain 0～10 % by weight.
As curing catalysts, can enumerate organo-tin compound, for example can enumerate stannous octoate, naphthenic acid tin, stearic acid tin, two sad dibutyl tins, dibutyl tin laurate, two tertiary monocarboxylic acid dioctyl tins, two triethoxy silicic acid dibutyl tins, two oil base oxysuccinic acid dibutyl tins, dibutyltin diacetate, 1, 1, 3, the 3-tetrabutyl-1, 3-dilauryl oxygen base carbonyl-distannoxane, the two oxyethyl group silicic acid dibutyl tins of oxygen base, dibutyltin oxide, the reactant of dibutyltin oxide and phthalic ester, the reactant of dibutyltin oxide and maleic acid diester, bis-acetylacetonate base dibutyl tin etc.As other organometallic compound, can enumerate carboxylic acid (such as sad) salt of bismuth, barium, calcium, indium, titanium, zirconium, calcium, zinc, iron, cobalt, lead etc., such as Bismuth Octoate, calcium octoate etc.They both can use separately, and also two or more kinds may be used.
The solidification compound that contains urethane resin of the present invention is made up of above-mentioned each composition, can be by these compositions are for example manufactured with the mixing such as high-speed stirring mixer, ball mill.
Above-mentioned solidification compound can be used as urethane resin and the disposable liquid type being obtained by mixing of aforementioned gradation composition; Or the base that contains urethane resin, with the binary liquid shape of the solidifying agent that contains curing catalysts; Or the three liquid types using the toning agent that comprises tinting material and softening agent etc. as an other composition use again.
In addition, above-mentioned solidification compound is in the situation that forming binary liquid shape, can be preferably 100: 0.5 to be selected from～at least 1 weight ratio in 20, more preferably 100: 1～15, more preferably 100: 5～10 scope, above-mentioned base is measured and mixed with above-mentioned solidifying agent, after making it to solidify, used.
Embodiment
, will enumerate embodiment and comparative example below, the present invention is carried out to more specific description, but the present invention is not subject to their any restriction.
[preparation of urethane resin]
Embodiment 1
Polyoxypropyleneglycol (PML-4013 processed of the Asahi Glass Urethane Co., Ltd.) 462g of the polyoxytrimethylene single methanol of number-average molecular weight 5000 (PML-S-1005 processed of Asahi Glass Co., Ltd) 458g, number-average molecular weight 13000, isophorone diisocyanate (firmly changing Bayer Desmodur I processed) 53g are mixed.This mixture is reacted 24 hours at 90 DEG C, obtain polyurethane prepolymer.
In this prepolymer 515g, drop into aminoethylamino propyl group methyl dimethoxysilane (KBM-602 processed of KCC of SHIN-ETSU HANTOTAI) 21g, at 30 DEG C, stir 30 minutes.Then, in this prepolymer, drop into the aminopropyl methyl dimethoxysilane (KBM-902 processed of KCC of SHIN-ETSU HANTOTAI) of 7.3g and the methyl alcohol of 0.3g, at 30 DEG C, stir after 30 minutes, obtain urethane resin.
Embodiment 2
Polyoxypropyleneglycol (PML-4013 processed of the Asahi Glass Urethane Co., Ltd.) 462g of the polyoxytrimethylene single methanol of number-average molecular weight 5000 (PML-S-1005 processed of Asahi Glass Co., Ltd) 458g, number-average molecular weight 13000, isophorone diisocyanate (firmly changing Bayer Desmodur I processed) 53g are mixed.This mixture is reacted 24 hours at 90 DEG C, obtain polyurethane prepolymer.
In this prepolymer 515g, drop into aminoethylamino propyl group methyltrimethoxy silane (KBM-603 processed of KCC of SHIN-ETSU HANTOTAI) 21g, at 30 DEG C, stir 30 minutes.Then, in this prepolymer, drop into the aminopropyl methyl dimethoxysilane (KBM-902 processed of KCC of SHIN-ETSU HANTOTAI) of 7.3g and the methyl alcohol of 0.3g, at 30 DEG C, stir after 30 minutes, obtain urethane resin.
Comparative example 1
Polyoxypropyleneglycol (PML-4011 processed of the Asahi Glass Co., Ltd) 500g of number-average molecular weight 10000 is reacted 42 hours under the condition of equivalence ratio=2.0 of NCO/OH with isophorone diisocyanate (firmly changing Bayer Urethane Desmodur I processed) at 90 DEG C, obtain polyurethane prepolymer.
In this prepolymer 444g, drop into aminoethylamino propyl group methyl dimethoxysilane (KBM-602 processed of KCC of SHIN-ETSU HANTOTAI) 51.3g.Add again ethyl acrylate 91.5g and stir after 10 days at 50 DEG C, obtaining urethane resin.
Comparative example 2
Polyoxypropyleneglycol (PML-4011 processed of the Asahi Glass Co., Ltd) 210g of number-average molecular weight 10000 is reacted 42 hours under the condition of equivalence ratio=2.0 of NCO/OH with isophorone diisocyanate (firmly changing Bayer Urethane Desmodur I processed) at 90 DEG C, obtain having the polyurethane prepolymer of the viscosity of 20000mPas at 20 DEG C.
In this prepolymer 104g, drop into aminoethylamino propyl group methyl dimethoxysilane (KBM-602 processed of KCC of SHIN-ETSU HANTOTAI) 8g.Stir after 30 minutes at 30 DEG C, obtain having the full-bodied urethane resin that cannot stir.
[preparations of 2 one-tenth somatotype solidification compounds]
Embodiment 3 and 4 and comparative example 3
Base
The cooperation goods, materials and equipments of the weight shown in table 1 is joined in the mixing and blending machine with heating and reliever, stir 30 minutes.Then, mix and blend 30 minutes at 60 DEG C is uniformly mixed 20 minutes under vacuum decompression, obtains base.
Solidifying agent
The curing catalysts of the weight shown in table 1, calcium carbonate are at room temperature mixed, and mix and blend 10 minutes, obtains solidifying agent.
The base of preparation is as described above mixed with 100: 10 (weight ratio) with solidifying agent, obtain solidification compound.
[table 1]
Unit: [g]
(note 1) Song Ben grease Co., Ltd. system, median size 60 μ m, Tg140 DEG C
(note 2) water-ground limestone, Shiraishi Calcium Kaisha Ltd.'s system " WHITON SB ", median size 3.7 μ m
(note 3) Marno Calcium Co., Ltd.'s system " Calfine 500 ", primary particle are 0.05 μ m, BET specific surface area 17m
2/ g
(note 4) DINP, New Japan Chem Co., Ltd's system " DINP "
(note 5) hindered amine is photostabilizer (HALS), Ciba company system " tinuvin 123 "
(note 6) Adeka of Co., Ltd. system " AO-60P "
(note 7) Johoku Chemical Co., Ltd.'s system " JF79 "
(note 8) divalent tin series catalysts, Nitto Kasei Co., Ltd's system " U-28 "
(note 9) 4 valency tin series catalysts, Nitto Kasei Co., Ltd's system " C-501 "
(note 10) amine series catalysts, Japan Oil Co's system " Amine BB "
The each urethane resin and the solidification compound that obtain preparing as described above, carried out following performance test.The results are shown in table 2 and table 3.
[method for testing performance]
1. viscosity
Use rotational viscosimeter (the digital viscometer of Brookfield company system), at 20 DEG C, measured preparation described above and the viscosity of urethane resin.
2. package stability
In constant temperature and humidity cabinet under the condition of 35 DEG C × 90%RH, to preparation described above and the package stability of urethane resin observed 24 hours.
3. evaluation of physical property
The upper barrier coating coating (trade(brand)name: Primer US-3: Sunstar Giken K. K.'s system) of the A5052P aluminium sheet (50 × 50 × 5mm) of regulation in JIS H 4000, set preparation described above and 2 one-tenth somatotype solidification compounds.After health (condition: 20 DEG C × 7 days+50 DEG C × 7 days), according to JIS A 14395.20 " stretching adhesive test " (2004), (20 DEG C × 7 days+50 DEG C × 7 days) after health in the early stage, measure 50% tensile stress [N/mm
2], maximum tensile stress [N/mm
2] and elongation [%] when ultimate load.
[table 2]
[table 3]
| Project | Embodiment 3 | Embodiment 4 | Comparative example 3 |
| Elongation (%) | 700 | 650 | 650 |
| 50% tensile stress [N/mm 2] | 0.13 | 0.14 | 0.30 |
| Maximum tensile stress [N/mm 2] | 0.51 | 0.46 | 0.75 |
In above result, the viscosity based on urethane resin of the present invention of manufacturing in embodiment 1 and 2 is 50,000～70,000mPas, and on the other hand, the not viscosity based on urethane resin of the present invention of manufacturing in comparative example 1 and 2 is more than 200,000.Thereby known: the disposal excellence based on urethane resin of the present invention.In addition we know: the package stability based on urethane resin of the present invention of manufacturing in embodiment 1 and 2 is good, on the other hand, the package stability of the urethane resin of manufacturing in comparative example 2 is abundant not.In addition, in embodiment 3 and 4, using 50% tensile stress of the solidification compound of manufacturing based on urethane resin of the present invention is 0.14N/mm
2below, maximum tensile stress is 0.51N/mm
2below, on the other hand, in comparative example 3, using 50% tensile stress of the solidification compound of not manufacturing based on urethane resin of the present invention is 0.30N/mm
2, maximum tensile stress is 0.75N/mm
2.Thereby known: by using based on urethane resin of the present invention, can to manufacture the more elastomerics of low modulus.
Claims (3)
1. a urethane resin, it is by making the compound in (1) carbamate prepolymer and (2) molecule with bridging property silyl, imino-and amino at NCO/NH
2the equivalence ratio scope that is 0.6～1.2 in reaction obtain,
By making, average terminal hydroxyl number is 1.3～2.1 to described (1) carbamate prepolymer, the mixture a of single methanol and polyvalent alcohol, and polymeric polyisocyanate b reaction obtains,
In described (2) molecule, there is bridging property silyl, imino-and amino compound and represented by following (formula 1),
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, R
1represent methyl or ethyl, R
2represent the alkyl of carbon number 2～10, R
3the alkyl that represents carbon number 2～10, n is 1,2 or 3,
Wherein,
The number-average molecular weight Mn of single methanol is 500～25000,
The number-average molecular weight Mn of polyvalent alcohol is 500～30000,
In the scope that is 1.6～2.5 in the equivalence ratio of NCO/OH, carry out the mixture a of single methanol and polyvalent alcohol, with the reacting of polymeric polyisocyanate b, and the mixture a of single methanol and polyvalent alcohol makes the single methanol of 20 % by weight～80 % by weight and the polyvalent alcohol of 20 % by weight～80 % by weight be obtained by mixing using this mixture a total amount as benchmark.
2. urethane resin according to claim 1, wherein,
Polyvalent alcohol is polyoxypropyleneglycol.
3. a manufacture method for urethane resin, is characterized in that,
Make the compound in (1) carbamate prepolymer and (2) molecule with bridging property silyl, imino-and amino at NCO/NH
2the equivalence ratio scope that is 0.6～1.2 in reaction, wherein,
By making, average terminal hydroxyl number is 1.3～2.1 to described (1) carbamate prepolymer, the mixture a of single methanol and polyvalent alcohol, and polymeric polyisocyanate b reaction obtains,
In described (2) molecule, there is bridging property silyl, imino-and amino compound and represented by following (formula 1),
(R
1o)
n-SiR
3-n-R
2-NH-R
3-NH
2(formula 1)
In formula, R represents methyl or ethyl, R
1represent methyl or ethyl, R
2represent the alkyl of carbon number 2～10, R
3the alkyl that represents carbon number 2～10, n is 1,2 or 3,
Wherein,
In the scope that is 1.6～2.5 in the equivalence ratio of NCO/OH, carry out the mixture a of single methanol and polyvalent alcohol, with the reacting of polymeric polyisocyanate b, and, the mixture a of single methanol and polyvalent alcohol makes the single methanol of 20 % by weight～80 % by weight and the polyvalent alcohol of 20 % by weight～80 % by weight be obtained by mixing using this mixture a total amount as benchmark
The number-average molecular weight Mn of single methanol is 500～25000,
The number-average molecular weight Mn of polyvalent alcohol is 500～30000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010060779A JP5769929B2 (en) | 2010-03-17 | 2010-03-17 | Polyurethane resin |
| JP2010-060779 | 2010-03-17 | ||
| PCT/JP2011/055080 WO2011114911A1 (en) | 2010-03-17 | 2011-03-04 | Polyurethane resin |
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| Publication Number | Publication Date |
|---|---|
| CN102791759A CN102791759A (en) | 2012-11-21 |
| CN102791759B true CN102791759B (en) | 2014-10-15 |
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ID=44649011
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|---|---|---|---|
| CN201180014077.9A Active CN102791759B (en) | 2010-03-17 | 2011-03-04 | Polyurethane resin |
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| Country | Link |
|---|---|
| US (1) | US8729194B2 (en) |
| EP (1) | EP2548903B1 (en) |
| JP (1) | JP5769929B2 (en) |
| CN (1) | CN102791759B (en) |
| MY (1) | MY159843A (en) |
| SG (1) | SG183926A1 (en) |
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| WO (1) | WO2011114911A1 (en) |
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| CN102448449B (en) * | 2009-05-29 | 2014-05-14 | 日本井上技术研究所株式会社 | Patch material |
| CN103421160A (en) * | 2012-05-25 | 2013-12-04 | 亨茨曼国际有限公司 | Polyurethane grouting composition |
| CN116836543A (en) * | 2023-07-09 | 2023-10-03 | 东莞市进升五金制品有限公司 | Preparation method of watch hardware key |
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| Publication number | Publication date |
|---|---|
| MY159843A (en) | 2017-02-15 |
| JP2011195617A (en) | 2011-10-06 |
| EP2548903B1 (en) | 2017-12-20 |
| EP2548903A1 (en) | 2013-01-23 |
| TWI526463B (en) | 2016-03-21 |
| US8729194B2 (en) | 2014-05-20 |
| TW201139481A (en) | 2011-11-16 |
| US20130035453A1 (en) | 2013-02-07 |
| WO2011114911A1 (en) | 2011-09-22 |
| SG183926A1 (en) | 2012-10-30 |
| EP2548903A4 (en) | 2013-08-21 |
| CN102791759A (en) | 2012-11-21 |
| JP5769929B2 (en) | 2015-08-26 |
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